TWI454498B - Curable resin composition, cured article thereof, print wiring board, epoxy resin and method for producing the same - Google Patents

Description

Curable resin composition, cured product thereof, printed wiring board, epoxy resin, and preparation method thereof

The present invention is excellent in heat resistance and low thermal expansion property of the obtained cured product, and can be suitably used for a curable resin composition such as a printed wiring board, a semiconductor sealing material, a coating material, or a casting application, a cured product thereof, and a novel epoxy resin. A printed wiring board excellent in resin, its production method, and heat resistance and low thermal expansion.

The epoxy resin is widely used in semiconductor sealing materials because it is excellent in heat resistance and moisture resistance, in addition to an adhesive, a molding material, a paint, a photoresist, a color developing material, and the like. Or electrical and electronic fields such as insulating materials for printed wiring boards.

Among these various applications, in the field of printed wiring boards, with the trend toward miniaturization and high performance of electronic devices, the semiconductor device has a tendency to increase in density by narrowing the wiring pitch, and it is a semiconductor corresponding thereto. In the encapsulation method, a flip chip connection method in which a semiconductor device is bonded to a substrate by solder balls is widely used. Since the flip chip connection method is a so-called reflow soldering semiconductor package in which solder balls are disposed between a wiring board and a semiconductor and is heated and integrated as a whole, the wiring board itself is exposed during solder reflow. In a high-heat environment, due to thermal contraction of the wiring board, a large stress is generated in the solder ball connecting the wiring board and the semiconductor, and connection failure of the wiring may occur. Therefore, the insulating material used in the printed wiring board is required to be a material having a low thermal expansion rate.

In addition, in recent years, high-melting-point solders that do not use lead have become mainstream because of the regulatory control of environmental problems. Because the lead-free solder is used at a temperature of about 20 to 40 ° C higher than that of the previous eutectic solder, the curable resin composition is Requires higher heat resistance than ever before.

In this way, the insulating material for a printed wiring board is required to have high heat resistance and low thermal expansion property. As an epoxy resin material corresponding to such a requirement, for example, the following structural formula is known.

The tetrafunctional naphthalene epoxy resin shown below (refer to Patent Document 1 below).

However, the tetrafunctional naphthalene epoxy resin has a higher crosslinking density than a normal phenol novolak epoxy resin, and exhibits excellent low thermal expansion property or heat resistance in an epoxy resin cured product. Higher performance is required in recent years and must be further improved. In addition, the solubility of the above-described tetrafunctional naphthalene epoxy resin in the solvent used for the usual production of a printed wiring board is low, and the properties of the cured product cannot be sufficiently remarkably exhibited.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Patent No. 3137202

Therefore, the problem to be solved by the present invention is to provide a curable resin composition which exhibits excellent heat resistance and low thermal expansion property and which can achieve good solvent solubility, and is excellent in cured product, heat resistance and low thermal expansion property. A printed wiring board, an epoxy resin that imparts these properties, and a method of making the same.

In order to solve the above problem, the inventors of the present invention have found that the reaction of the 2,7-dihydroxynaphthalene with formaldehyde under specific conditions, and then the reaction of the obtained reactant with epichlorohydrin has a carbonyl group. The epoxy resin exhibits excellent heat resistance, low thermal expansion property, and good solvent solubility, and the present invention has been completed.

That is, the present invention relates to a curable resin composition characterized by an epoxy resin (A) having a naphthalene structure and a hardener (B) as an essential component. a skeleton formed by a methylene group bonded to a cyclohexadienone structure, and a glycidoxy group.

Further, the present invention relates to a cured product characterized in that the curable resin composition is hardened and reacted.

Moreover, the present invention relates to a printed wiring board which is immersed in a glass woven fabric by a resin composition containing an epoxy resin (A), a curing agent (B), and an organic solvent (C) as essential components. The copper foil is laminated and heated and pressure-bonded, wherein the epoxy resin (A) has a skeleton in which a naphthalene structure and a cyclohexadienone structure are bonded through a methylene group in a molecular structure, and a propylene oxide group. Oxygen.

Further, the present invention relates to an epoxy resin characterized by having a skeleton in which a naphthalene structure and a cyclohexadienone structure are bonded through a methylene group and a glycidoxy group in a molecular structure.

Further, the present invention relates to an epoxy resin characterized by having 2,7-dihydroxynaphthalenes and formaldehyde in an amount of 0.2 to 2.0 times based on the molar basis with respect to 2,7-dihydroxynaphthalenes. Molecular structure obtained by reacting the obtained reactant with epihalohydrin in the presence of a basic catalyst.

Moreover, the present invention relates to a process for producing an epoxy resin characterized in that 2,7-dihydroxynaphthalenes and formaldehyde are 0.2 to 2.0 times based on the molar reference with respect to 2,7-dihydroxynaphthalenes. The reaction is carried out in the presence of an amount of a basic catalyst, and then the resulting reactant is reacted with an epihalohydrin.

According to the present invention, it is possible to provide a curable resin composition which exhibits excellent heat resistance and low thermal expansion property, and which is excellent in solvent solubility, and a printed wiring board excellent in heat resistance and heat expansion property. These properties of epoxy resin, and its preparation method.

Hereinafter, the present invention will be described in detail.

The epoxy resin (A) used in the present invention is characterized in that it has a skeleton in which a naphthalene structure and a cyclohexadienone structure are linked by a methylene group and a glycidoxy group in a molecular structure. That is, since the skeleton having a naphthalene structure and a cyclohexadienone structure transmitted through a methylene group in a molecular structure, a chemical solvent asymmetry of the epoxy resin (A) can exhibit good solvent solubility. . Further, in the curing reaction of the epoxy group and the curing agent, the cyclohexadienone structure participates in the curing reaction, whereby a strong cured product can be obtained, and the heat resistance and low thermal expansion property of the cured product are improved.

Here, the cyclohexadienone structure system specifically includes the following structural formulas k1 and k2. The 2,4-cyclohexadienone structure shown, and the following structural formula k3

The 2,5-cyclohexadienone structure shown.

Among these, the 2,4-cyclohexadienone structure represented by the above structural formulas k1 and k2 is preferably excellent in heat resistance and low thermal expansion property, and is represented by the above structural formula k1. The naphthalenone structure is particularly preferred.

The epoxy resin (A) can be reacted by reacting 2,7-dihydroxynaphthalenes and formaldehyde in the presence of a basic catalyst, and then reacting the obtained reactants with epihalohydrin (method) 1), or a method of reacting 2,7-dihydroxynaphthalenes and formaldehyde and phenols in the presence of a basic catalyst, and then reacting the obtained reactants with epihalohydrin (method 2) Manufactured, it is possible to contain an epoxy resin having various molecular structures, and specifically, a structure having a structure in which a naphthalene structure and a cyclohexadienone structure represented by the above structural formula k1 or k2 are bonded through a methylene group is used as a basic skeleton. And a compound (a) having a glycidoxy group as a substituent on the aromatic ring is preferred.

Specific examples of such a compound (a) include the following structural formulae (i) to (iii).

In the above structural formulae (i) to (iii), R ¹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and specifically, the above structural formula ( The compounds shown in i) include the following i-1 to i-8.

In addition, examples of the compound represented by the above structural formula (ii) include the following ii-1 to ii-8.

In addition, examples of the compound represented by the above structural formula (iii) include the following iii-1 to iii-8.

Among these, in particular, the following structural formula (i)

(wherein R ¹ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms), and the heat resistance and the low thermal expansion property are remarkably excellent. Words are especially good. The compound represented by the above structural formula (i) is as described above, and has a cyclohexadienone structure in its molecular structure, so that it is chemically structurally asymmetric and can exhibit excellent solvent solubility, and cyclohexadiene. Since the ketone structure itself contributes to the hardening reaction with the hardener (B), the compound represented by the above structural formula (i) exhibits excellent heat resistance and low thermal expansion property despite being a trifunctional epoxy resin.

In the present invention, among these, particularly in terms of high heat resistance, all of the hydrogen atoms in the R ₁ system of the formula (1) have the following structural formula (i-α).

The structure shown is preferred.

When the epoxy resin (A) detailed above is produced by the above method 1 or method 2, since the compound (iv) below is usually produced in addition to the above compound (a)

The compound (b) shown, or the aromatic ring of the above structural formula (i), the above structural formula (ii) or the above structural formula (iii), and further the following structural formula (v)

The epoxy resin oligomer (c) bonded to the structural moiety shown, and because the oligomer (d) is also formed in the above method 1 or method 2 when reacting with the epihalohydrin, the present invention The epoxy resin (A) can also be used as a mixture of these.

In the epoxy resin (A), the compound (a) is preferably contained in an amount of from 5.0 to 20.0% by mass, and specifically, the compound is contained in an amount of from 5.0 to 20.0% by mass in terms of excellent solvent solubility. (a) The compound (b) of the above-mentioned oligomer (c) or the oligomer (d) is preferably contained in a ratio of from 15.0 to 50.0% by mass of the above compound (b) and from 30 to 80% by mass. .

Further, in terms of heat resistance and low thermal expansion property, the epoxy resin (A) preferably has an epoxy equivalent in the epoxy resin (A) in the range of 150 to 300 g/eq, and preferably 155 to 250 g/eq. The range is particularly good.

As described above, the epoxy resin (A) can be produced by the above method 1 or method 2, which is characterized in that the amount of the alkaline catalyst is larger than that of the prior art, specifically, relative to 2, 7-two. The molar number of the hydroxynaphthalene or the total number of moles of the 2,7-dihydroxynaphthalenes and the phenols, and the molecular structure can be obtained by using an alkaline catalyst in an amount of 0.2 to 2.0 times based on the molar basis. A skeleton formed by a naphthalene structure and a cyclohexadienone structure linked through a methylene group. In contrast, the following structural formula of the well-known compound (2)

The compound shown can be produced by using a basic catalyst in a ratio of 0.01 to 0.1 times the molar ratio of 2,7-dihydroxynaphthalene and formaldehyde to 2,7-dihydroxynaphthalene and formaldehyde. However, in the case of such a catalyst amount, the cyclohexadienone structure of the present invention is not produced because the compound represented by the structural formula (2) is selectively formed and precipitated in the process and the reaction is stopped.

Here, the 2,7-dihydroxynaphthalene used in the method 1 or the method 2 may, for example, be 2,7-dihydroxynaphthalene, methyl-2,7-dihydroxynaphthalene or ethyl-2,7-di Hydroxynaphthalene, tert-butyl-2,7-dihydroxynaphthalene, methoxy-2,7-dihydroxynaphthalene, ethoxy-2,7-dihydroxynaphthalene, and the like.

In the formaldehyde used in the method 1 or the method 2, the formaldehyde may be a solution of a formalin in an aqueous solution or a polyoxymethylene in a solid state.

Further, examples of the phenol used in the method 2 include phenol, o-cresol, p-cresol, 2,4-xylenol, and the like.

Moreover, the alkaline catalyst used in the method 1 or the method 2 may, for example, be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, sodium metal, lithium metal, sodium hydride, sodium carbonate or potassium carbonate. Inorganic bases, etc.

As described above, in the above-mentioned compound (a), the compound represented by the above structural formula (i) is preferred. Therefore, among the above methods, the method of the method 1 is preferred. Hereinafter, the method 1 will be described in detail.

In the above method 1, specifically, a method in which 2,7-dihydroxynaphthalene (a) and formaldehyde are substantially simultaneously added and heated and stirred in the presence of a suitable catalyst to carry out a reaction; A method in which a mixture of 7-dihydroxynaphthalenes (a) and a suitable catalyst is continuously or intermittently added to the system to carry out a reaction. Further, here, substantially simultaneously, it means that all the raw materials are added during the period in which the reaction is accelerated by heating.

Examples of the alkaline catalyst used herein include an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an inorganic base such as sodium metal, lithium metal, sodium hydride, sodium carbonate or potassium carbonate. . The amount of use is as described above, and the molar number of the 2,7-dihydroxynaphthalene (a) is preferably in the range of 0.2 to 2.0 times based on the molar standard.

The reaction ratio of the 2,7-dihydroxynaphthalene (a) to formaldehyde is not particularly limited, and the formaldehyde of the 2,7-dihydroxynaphthalene is 0.6 to 2.0 times based on the molar standard, and heat resistance is obtained. The balance of the viscosity of the epoxy resin is excellent, and the ratio is preferably 0.6 to 1.5 times.

When this reaction is carried out, an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include methyl stilbene, isopropyl alcohol, ethyl siroli, toluene, xylene, and methyl isobutyl ketone, but are not limited thereto. The amount of the organic solvent to be used is usually in the range of 0.1 times to 5 times the total mass of the raw material to be added, and the structure of the structural formula (i) can be efficiently obtained, and the amount is 0.3 times to 2.5. The range of the multiple is particularly good. Further, the reaction temperature is preferably in the range of 20 to 150 ° C, particularly preferably in the range of 60 to 100 ° C. Further, the reaction time is not particularly limited, but is usually in the range of 1 to 10 hours.

After completion of the reaction, neutralization or water washing treatment is carried out until the pH of the reaction mixture is 4 to 7. The neutralization treatment or the water washing treatment can be carried out in accordance with a usual method. For example, when an alkaline catalyst is used, an acidic substance such as acetic acid, phosphoric acid or sodium phosphate can be used as a neutralizing agent. After the neutralization or the water washing treatment, the organic solvent is distilled off under reduced pressure and the product is concentrated to obtain a carbonyl group-containing phenol compound. Further, in the case where the inorganic salt or the foreign matter can be purified and removed, it is more preferable to introduce a precision filtration process in the treatment operation after the completion of the reaction.

Subsequently, the target phenol compound (A) can be obtained by reacting the obtained phenol compound with formaldehyde. Specifically, for example, an epihalohydrin having a ratio of 2 to 10 times (mole basis) is added to the molar number of the phenolic hydroxyl group in the phenol compound, and the number of moles relative to the phenolic hydroxyl group is further increased. The alkaline catalyst of 0.9 to 2.0 times (mole basis) is added in a batch or slowly, and is reacted at a temperature of 20 to 120 ° C for 0.5 to 10 hours. The alkaline catalyst may be a solid or an aqueous solution thereof. When an aqueous solution is used, water and epihalohydrin may be continuously supplied from the reaction mixture under reduced pressure or under normal pressure while continuously adding. A method of distilling off, further separating the liquid to remove water and continuously returning the epihalohydrin to the reaction mixture.

Further, in industrial production, all of the epihalohydrin-based novels used in the initial batching of the epoxy resin are added, but after the next batch, the epihalohydrins recovered from the crude reaction product are used in combination. It is preferred that the novel epihalohydrin is used in the amount consumed by the reaction. In this case, the epihalohydrin to be used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin. Among them, epichlorohydrin is preferred because it is industrially easy to obtain.

Further, the alkaline catalyst may specifically be an alkaline earth metal hydroxide, an alkali metal carbonate or an alkali metal hydroxide. In particular, in view of excellent catalyst activity of the epoxy resin synthesis reaction, an alkali metal hydroxide is preferable, and examples thereof include sodium hydroxide and potassium hydroxide. These alkaline catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in the form of a solid. Further, the reaction rate at the time of synthesizing the epoxy resin can be improved by using an organic solvent in combination. The organic solvent is not particularly limited, and examples thereof include ketones such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, second butanol, and third butyl. Alcohols such as alcohols, methyl serotonin, ethyl serotonin, etc., cyclamate, tetrahydrofuran, 1,4-two Alkane, 1,3-two An ether such as an alkane or diethoxyethane; an aprotic polar solvent such as acetonitrile, dimethyl hydrazine or dimethylformamide. Each of these organic solvents may be used singly or in combination of two or more kinds in order to adjust the polarity.

After the reactant of the epoxidation reaction is washed with water, the unreacted epihalohydrin or the organic solvent used in combination is distilled off by heating under reduced pressure and distillation. Further, in order to further use an epoxy resin having less water-decomposable halogen, the obtained epoxy resin may be dissolved in an organic solvent such as toluene, methyl isobutyl alcohol or methyl ethyl ketone, and sodium hydroxide may be added thereto. Further, an aqueous solution of an alkali metal oxide such as potassium hydroxide is further reacted. At this time, in order to increase the reaction rate, a related mobile catalyst such as a quaternary ammonium salt or a crown ether may be present. When the relevant mobile catalyst is used, the amount thereof is preferably 0.1 to 3.0 parts by mass based on 100 parts by mass of the epoxy resin used. After the completion of the reaction, the resulting salt is removed by filtration, washing with water, or the like, and a solvent such as toluene or methyl isobutyl ketone is distilled off under reduced pressure to obtain an epoxy resin (A) containing the target compound (a). ).

In the curable resin composition of the present invention, the epoxy resin (A) may be used singly or other epoxy resins may be used insofar as the effects of the present invention are not impaired. Specifically, the epoxy resin (A) is 30% by mass or more based on the total mass of the epoxy resin component, and it is preferable to use another epoxy resin in a range of 40% by mass or more.

As another epoxy resin which can be used together with the epoxy resin (A), various epoxy resins can be used, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, and biphenyl epoxy. Resin, tetramethylbiphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl Ethylene glycol type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin , naphthol-phenol co-phenolic varnish type epoxy resin, naphthol-cresol copolyphenolic varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl aldehyde varnish type epoxy resin Wait. Among these epoxy resins, a phenol aralkyl type epoxy resin, a biphenyl aldehyde varnish type epoxy resin, or a naphthol novolak containing a naphthalene skeleton can be used for obtaining a cured product excellent in flame retardancy. Epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol copolyphenolic epoxidized epoxy resin, naphthol-cresol copolyphenolic epoxidized epoxy resin, or crystalline biphenyl ring Oxygen resin, tetramethylbiphenyl type epoxy resin, (xanthene) type epoxy resin or alkoxy-containing aromatic ring modified novolac type epoxy resin (a compound obtained by linking an epoxy ring containing an epoxy group to an aromatic ring containing an alkoxy group) It is especially good.

In addition, the curing agent (B) used in the curable resin composition of the present invention may be a curing agent such as an amine compound, a guanamine compound, an acid anhydride compound or a phenol compound. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl hydrazine, isophorone diamine, imidazole, and BF ₃ -amine. Examples of the amide-based compound include dicyanodiamine, a polyamine resin obtained by synthesizing a dimer of linolenic acid and ethylenediamine, and the like. Examples of the acid anhydride-based compound include phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyrogalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic acid (nadic). An acid anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, etc., and examples of the phenol compound include a phenol novolak resin, a cresol novolak resin, an aromatic hydrocarbon formaldehyde resin modified phenol resin, and a bicyclobenzenediene. Phenol addition resin, phenol aralkyl resin (XYLOCK resin), naphthol aralkyl resin, trimethylolethane resin, tetraphenol ethane resin, naphthol novolac resin, naphthol-phenol copolyphenol novolak Resin, naphthol-cresol copolyphenolic varnish resin, biphenyl modified phenol resin (by Shuangya Polyhydric phenolic compound having phenolic ring formed by coupling), biphenyl-modified naphthol resin (polyhydric naphthol compound linked by methylene bis phenolic ring formed), three amine Modified phenol resin (polyphenolic compound formed by linking a phenol ring such as melamine or benzoguanamine) or an alkoxy-containing aromatic ring-modified novolak resin (by a formaldehyde-linked phenol ring and an alkoxy group) A polyphenol compound such as a polyhydric phenol compound).

Among these, in terms of low thermal expansion property, it is particularly preferable to contain a large amount of an aromatic skeleton in a molecular structure. Specifically, since it has excellent low thermal expansion property, a phenol novolak resin, a cresol novolak resin, and a fragrance are used. Alkaloid formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolac resin, naphthol-phenol copolyphenolic varnish resin, naphthol-cresol copolyphenolic varnish resin, Benzene modified phenol resin, biphenyl modified naphthol resin, amine based A modified phenol resin or an alkoxy-containing aromatic ring-modified novolac resin (a polyphenol compound obtained by linking a phenol ring and an alkoxy-containing aromatic ring with formaldehyde) is preferred.

The amount of the epoxy resin (A) and the curing agent (B) in the curable resin composition of the present invention is not particularly limited, and the obtained cured product is excellent in terms of the epoxy resin (A). The total amount of the epoxy groups is preferably 1 equivalent, and the active group in the hardener (B) is preferably in the range of 0.7 to 1.5 equivalents.

Further, a curing accelerator may be used in combination as appropriate in the curable resin composition of the present invention. Various materials can be used as the hardening accelerator, and examples thereof include a phosphorus compound, a third amine, an imidazole, an organic acid metal salt, a Lewis acid, and an amine salt. In particular, when it is used as a semiconductor sealing material, the phosphorus compound is excellent in hardenability, heat resistance, electrical properties, moisture resistance, etc., and the phosphorus compound is triphenylphosphine, and the third amine is 1,8-diaza Bicyclo [5.4.0]-undecene (DBU) is preferred.

The curable resin composition of the present invention described in detail above is characterized in that it exhibits excellent solvent solubility. Therefore, it is preferable that the curable resin composition is prepared by mixing the organic solvent (C) in addition to the above respective components. Examples of the organic solvent (C) which can be used herein include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, and methyl race. Su, ethylene glycol acetate, propylene glycol monomethyl ether acetate, etc., the selection and the appropriate amount of use can be appropriately selected according to the use, for example, in the case of printed wiring board, methyl ethyl ketone, acetone, A polar solvent having a boiling point of 160 ° C or less, such as dimethylformamide, is preferred, and a nonvolatile content of 40 to 80% by mass is preferably used. On the other hand, when it is used for the adhesive film for assembly, as the organic solvent (C), for example, a ketone such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, celecoxib acetate or propylene glycol can be used. Acetate such as monomethyl ether acetate or carbitol acetate, carbitol such as celecoxib or butyl carbitol, aromatic hydrocarbon such as toluene or xylene, or dimethyl Mercuryamine, dimethylacetamide, N-methylpyrrolidone, etc. are preferred, and it is preferably used in a ratio of 30 to 60% by mass.

In addition, in the field of a printed wiring board, the thermosetting resin composition can be blended with a non-halogen which does not substantially contain a halogen atom, for example, in the field of a printed wiring board. Burning agent.

Examples of the non-halogen-based flame retardant include a phosphorus-based flame retardant, a nitrogen-based flame retardant, a barium-based flame retardant, an inorganic flame retardant, and an organic metal salt-based flame retardant. It is not particularly limited and may be used singly or in combination with a flame retardant of the same system or a combination of different flame retardants.

As the phosphorus-based flame retardant, any of an inorganic system and an organic system can be used. The inorganic compound may, for example, be an inorganic nitrogen-containing phosphorus compound such as ammonium phosphate such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate or ammonium polyphosphate, or guanidinium phosphate.

Further, in order to prevent hydrolysis or the like, the red phosphorus is preferably subjected to surface treatment, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and cerium oxide. a method of coating treatment with an inorganic compound such as cerium hydroxide, cerium nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide, and a phenol resin a method of coating a mixture of a thermosetting resin, and (iii) using a thermosetting resin such as a phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide. Double coating method, etc.

Examples of the organophosphorus compound include a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphorane compound, a general organic phosphorus compound such as an organic nitrogen-containing phosphorus compound, and 9,10-di. Hydrogen-9-oxa-10-phosphaphene=10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphene=10-oxide, 10-( a cyclic organophosphorus compound such as 2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphene=10-oxide, and reacted with a compound such as an epoxy resin or a phenol resin Derivatives, etc.

The blending amount can be appropriately selected according to the type of the phosphorus-based flame retardant, the components other than the curable resin composition, and the degree of flame retardancy required, for example, with respect to blending an epoxy resin, a hardener, or When 100 parts by mass of the curable resin composition, such as a halogen-based flame retardant and other fillers or additives, is used, it is preferable to use red phosphorus as a non-halogen flame retardant in the range of 0.1 to 2.0 parts by mass. When the organophosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly preferably in the range of 0.5 to 6.0 parts by mass.

Further, when the phosphorus-based flame retardant is used, the phosphorus-based flame retardant may be hydrotalcite, magnesium hydroxide, a boron compound, zirconia, black dye, calcium carbonate, zeolite, zinc molybdate, or active. Carbon, etc.

Examples of the nitrogen-based flame retardant include, for example, three Compound, cyanuric acid compound, isocyanuric acid compound, thiophene Wait, to three Compounds, cyanuric acid compounds, and isocyanuric acid compounds are particularly preferred.

As the aforementioned three The compound may, for example, be melamine, acetamide, benzoguanamine, trimeric dicyandiacetonitrile, melam, succinimide, ethyl bismelamine, melamine polyphosphate, tridecylamine, etc., and, for example, i) Sulfate-based melamine sulfate, melemide sulfate, melamamine sulfate, etc. a compound; (ii) a phenol such as phenol, cresol, xylenol, butylphenol or nonylphenol; and a melamine such as melamine, benzoguanamine, acetamide or formamide; a cocondensate; (iii) a mixture of the condensate of the above (ii) and a phenol resin such as a phenol formaldehyde condensate; (iv) the use of the above (ii) or (iii) for the use of tung oil, anisotropic linseed oil, or the like. Modified by the like.

Specific examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.

The blending amount of the nitrogen-based flame retardant can be appropriately selected depending on the type of the nitrogen-based flame retardant, the components other than the curable resin composition, and the degree of necessity of flame retardancy. For example, the epoxy resin is blended with the epoxy resin. 100 parts by mass of the curable resin composition, such as a hardener, a non-halogen-based flame retardant, and other fillers or additives, is preferably blended in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass. The range is well matched.

Further, when the nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound or the like may be used in combination.

The antimony-based flame retardant is not particularly limited as long as it is an organic compound containing a ruthenium atom, and examples thereof include eucalyptus oil, ruthenium rubber, and ruthenium resin.

The blending amount of the antimony-based flame retardant can be appropriately selected depending on the type of the antimony-based flame retardant, the components other than the curable resin composition, and the degree of necessity of flame retardancy, for example, with respect to blending epoxy resin. In 100 parts by mass of the curable resin composition, which is a hardener, a non-halogen-based flame retardant, and other fillers or additives, it is preferably blended in an amount of 0.05 to 20 parts by mass. Further, when the above-mentioned lanthanum-based flame retardant is used, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include a metal hydroxide, a metal oxide, a metal carbonate compound, a metal powder, a boron compound, and a low melting point glass.

Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

Specific examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and oxidation. Cobalt, cerium oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide, and the like.

Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, rhodium, chromium, nickel, copper, tungsten, tin, and the like.

Specific examples of the boron-based compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting glass include SIPURI (Bokusui Brown Co., Ltd.), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O ₅ -MgO system, and P. Glass such as ₂ O ₅ -B ₂ O ₃ -PbO-MgO system, P-Sn-OF system, PbO-V ₂ O ₅ -TeO ₂ system, Al ₂ O ₃ -H ₂ O system, or lead borosilicate Compound.

The blending amount of the inorganic flame retardant can be appropriately selected depending on the type of the inorganic flame retardant, the components other than the curable resin composition, and the degree of necessity of flame retardancy, for example, with respect to blending an epoxy resin. In 100 parts by mass of the curable resin composition, which is a hardener, a non-halogen-based flame retardant, and other fillers or additives, it is preferably blended in an amount of 0.05 to 20 parts by mass. It is particularly preferable to mix in the range of 0.5 to 15 parts by mass.

Examples of the organometallic salt-based flame retardant include ferrocene, an acetoacetone metal complex, an organometallic carbonyl compound, an organic cobalt salt compound, an organic sulfonic acid metal salt, a metal atom and an aromatic compound or A compound in which a heterocyclic compound is ion-bonded or coordinately bonded.

The blending amount of the organometallic salt flame retardant can be appropriately selected depending on the type of the organometallic salt flame retardant, the components other than the curable resin composition, and the degree of necessity of flame retardancy, for example, relative to the blending epoxy In 100 parts by mass of the curable resin composition, which is a resin, a hardener, a non-halogen-based flame retardant, and other fillers or additives, it is preferably blended in a range of 0.005 to 10 parts by mass.

In the curable resin composition of the present invention, an inorganic filler may be blended as necessary. Examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, and aluminum hydroxide. When the amount of the above inorganic filler is particularly large, it is preferred to use molten cerium oxide. The molten cerium oxide may be either a crushed or a spherical shape. In order to increase the amount of molten cerium oxide and suppress the increase in the melt viscosity of the molding material, it is preferred to use a spherical shape. Further, in order to increase the blending amount of the spherical cerium oxide, it is preferred to appropriately adjust the particle distribution of the spherical cerium oxide. The filling rate is preferably high in flame retardancy, and is preferably 20% by mass or more based on the total amount of the curable resin composition. Moreover, when it is used for the use of a conductive paste or the like, a conductive filler such as silver powder or copper powder can be used.

The curable resin composition of the present invention may contain various compounding agents such as a decane coupling agent, a releasing agent, a pigment, and an emulsifier as necessary.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components. The method of obtaining the cured product of the present invention from the curable resin composition described in detail above may be carried out according to the curing method of the usual curable resin composition, and may be appropriately selected depending on the type, use, and the like of the combined curing agent. The heating temperature condition may be, for example, a method of heating the curable resin composition of the present invention to a temperature range of 20 to 250 °C. Examples of the form of the cured product include a laminate, a cast material, an adhesive layer, a coating film, and a film.

Examples of the use of the curable resin composition of the present invention include a printed wiring board material, a photoresist ink, a conductive paste, an interlayer insulating material for an assembly substrate, an adhesive film for assembly, a resin casting material, and an adhesive.

In the application of the printed wiring board or the adhesive film for assembly, it is possible to use a so-called electronic component internal storage substrate in which an active component such as a capacitor or a passive component such as an IC chip is embedded in the substrate. Insulation Materials. Among these, the characteristics of high heat resistance, low thermal expansion property, and solvent solubility are preferably used as a printed wiring board material, a photoresist ink, a conductive paste, an interlayer insulating material for an assembly substrate, and an adhesive film for assembly. . In particular, the solvent solubility of the epoxy resin itself is drastically improved, and the heat resistance and low thermal expansion property of the cured product can be exhibited, and it is preferable to use it for a printed wiring board material.

Here, the printed wiring board of the present invention can be obtained by immersing a varnish-like curable resin composition containing the organic solvent (C) on a reinforcing substrate, laminating a copper foil, and heating and pressure-bonding it. Here, examples of the reinforcing substrate that can be used include paper, glass cloth, glass nonwoven fabric, aromatic polyamidamine paper, aromatic polyamide cloth, glass fiber board, and long-fiber glass fiber bundle cloth. When the method is described in detail, first, the varnish-like curable resin composition is heated at a temperature of 50 to 170 ° C depending on the heating temperature of the solvent to be used. That is, the prepreg. The mass ratio of the resin composition to the reinforcing substrate used in the present invention is not particularly limited, and the resin composition in the prepreg is preferably prepared in an amount of 20 to 60% by mass. Subsequently, the prepreg obtained as described above is laminated according to a usual method, and the appropriate copper foil is superposed and heated and pressed at 170 to 250 ° C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. A printed wiring board as a target can be obtained.

Subsequently, in the various applications described above, for example, a method of producing a photoresist ink may be, for example, a cationic polymerization catalyst as a curing agent (B) of the above-mentioned curable resin composition, and addition of a pigment, a talc, and a filler. A method of becoming a target photoresist ink. As the method of use, there is a method in which the photoresist ink obtained as described above is applied to a printed circuit board by screen printing, and is used as a cured photoresist.

The method of producing a conductive paste from the curable resin composition of the present invention is, for example, a method of dispersing fine conductive particles in the curable resin composition as a composition for an anisotropic conductive film, and at room temperature. A method of connecting a paste resin composition or an isotropic conductive adhesive to a liquid circuit.

In addition, the interlayer insulating material for the assembled substrate can be obtained by appropriately mixing a filler or the like in the curable resin composition. When the assembled substrate is produced by using the same, the curable resin composition is applied to a wiring board on which a circuit is formed by a spray coating method or a curtain flow coating method, and then cured. Then, it is necessary to perform perforation of a through hole or the like as required, and then the surface of the through hole is treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and metal such as copper is treated. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include an oxidizing agent, a base, an organic solvent, and the like. This operation is repeated in this order as needed, and a resin insulating layer and a conductive layer having a predetermined circuit pattern are formed by alternately assembling, whereby an assembled substrate can be obtained. However, the perforation of the through-hole portion is performed after the resin insulating layer of the outermost layer is formed. In addition, the resin-attached copper foil obtained by semi-hardening the resin composition on the copper foil is heat-pressed at 170 to 250 ° C on the wiring board on which the circuit is formed, and the formation of the roughened surface can be omitted. And a plating process to manufacture an assembled substrate.

The method for producing an adhesive film for assembly from the curable resin composition of the present invention is, for example, a method of applying the resin film of the present invention to a support film to form a resin film for use in a multilayer printed wiring board.

When the curable resin composition of the present invention is used for an adhesive film for assembly, the adhesive film is softened under lamination temperature conditions (usually 70 ° C to 140 ° C) of a vacuum lamination method, and laminated on a circuit board. At the same time, it is important to show that the resin can fill the flow holes (resin flow) existing in the via holes or the through holes of the circuit board, and it is preferable to formulate the above components to exhibit such characteristics.

Here, the through-hole of the multilayer printed wiring board has a diameter of usually 0.1 to 0.5 mm and a depth of usually 0.1 to 1.2 mm, and it is usually preferable to be able to fill the resin in this range. Moreover, when laminating both surfaces of a circuit board, it is preferable to fill about 1/2 of a through-hole.

In the method of producing the above-mentioned adhesive film, specifically, the varnish-like composition of the present invention can be applied to the surface of the support film (Y) by preparing a varnish-like curable resin composition, and further, by heating or blowing hot air. It is produced by drying the organic solvent to form a layer (X) of a curable resin composition.

The thickness of the layer (X) to be formed is usually set to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer having the circuit substrate is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

Further, the layer (X) of the present invention can also be protected by a protective film described later. By using a protective film for protection, it is possible to prevent dust from adhering to the surface of the resin composition layer or scratches.

Examples of the support film or the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, and polyethylenes such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate. Polycarbonate, polyimide, metal foil such as release paper or copper foil, aluminum foil, or the like. Further, the support film and the protective film may also be subjected to a matting treatment, a corona treatment, and a release treatment.

Further, the thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm is used. Further, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) is peeled off after being laminated on a circuit board or formed by an insulating layer by heat curing. When the adhesive film is heat-hardened and the support film (Y) is peeled off, it is possible to prevent dust or the like from adhering to the hardening step. When peeling after hardening, it is common to perform a mold release process in advance on a support film.

Subsequently, a method of manufacturing a multilayer printed wiring board using the adhesive film obtained as described above, for example, when the layer (X) is protected by the protective film, is peeled off to directly contact the layer (X) with the circuit substrate. The method is laminated on one or both sides of the circuit substrate, for example, by vacuum lamination. The layering method may be a batch type or a continuous type using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The lamination conditions are preferably such that the pressure-bonding temperature (lamination temperature) is 70 to 140 ° C, and the pressure-sensitive adhesive pressure is 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). Preferably, lamination is carried out under reduced pressure of 20 mmHg (26.7 hPa) or less.

[Examples]

Hereinafter, the examples and the comparative examples will be more specifically described. In the following, "parts" and "%" are based on quality unless otherwise notified. Further, the melt viscosity at 150 ° C and the GPC, NMR, and MS spectra were measured under the following conditions.

1) Melt viscosity at 150 ° C: in accordance with ASTM D4287

2) Softening point measurement method: JIS K7234

3) GPC: The measurement conditions are as follows.

Measuring device: "HLC-8220 GPC" column manufactured by TOSOH Co., Ltd.: GUARD COLUMN "H _XL -L" manufactured by TOSOH Co., Ltd.

+TSK-GEL G2000HXL, manufactured by TOSOH AG

+TSK-GEL G2000HXL, manufactured by TOSOH AG

+TSK-GEL G3000HXL made by TOSOH Co., Ltd.

+TSK-GEL G4000HXL made by TOSOH AG

Detector: RI (differential refraction diameter)

Data Processing: "GPC-8020 Type II Version 4.10" made by TOSOH Co., Ltd.

Measurement conditions: column temperature 40 ° C

Developing solvent tetrahydrofuran

Flow rate 1.0 ml / min

Standard: According to the above-mentioned "GPC-8020 Type II Edition 4.10" measurement manual, and the molecular weight is a known monodisperse polystyrene described below.

(using polystyrene)

"A-500" made by TOSOH Co., Ltd.

"A-1000" made by TOSOH Co., Ltd.

"A-2500" made by TOSOH Co., Ltd.

"A-5000" made by TOSOH AG

"F-1" made by TOSOH Co., Ltd.

"F-2" made by TOSOH Co., Ltd.

"F-4" made by TOSOH Co., Ltd.

"F-10" made by TOSOH AG

TOFOH AG "F-20"

"F-40" made by TOSOH Co., Ltd.

"F-80" made by TOSOH Co., Ltd.

"F-128" made by TOSOH Co., Ltd.

Sample: A tetrahydrofuran solution in which the solid content of the resin was 1.0% by mass was filtered using a precision filter (50 μl).

4) NMR: NMR GSX270 manufactured by Nippon Electronics Co., Ltd.

5) MS: manufactured by Nippon Electronics Co., Ltd. Double Convergence Mass Analyzer AX505H (FD505H)

Example 1

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 240 parts (1.50 mol) of 2,7-dihydroxynaphthalene, 85 parts (1.05 mol) of 37% by mass aqueous formaldehyde solution, and 376 parts were added. Isopropyl alcohol, 88 parts (0.75 mol) of a 48% aqueous potassium hydroxide solution, and stirred while blowing nitrogen gas at room temperature. Subsequently, the temperature was raised to 75 ° C and stirred for 2 hours. After completion of the reaction, 108 parts of soda primary phosphate was added and neutralized, and then isopropyl alcohol was removed under reduced pressure, and 480 parts of methyl isobutyl ketone was added. After the obtained organic layer was washed three times with 200 parts of water, the methyl isobutyl ketone was removed under heating and reduced pressure to obtain 245 parts of a phenol compound (A-1). The hydroxyl group equivalent of the obtained phenol compound (A-1) was 84 g/eq. The GPC chart of the obtained phenol compound is shown in Fig. 1, the C ¹³ NMR chart is shown in Fig. 2, and the MS spectrum is shown in Fig. 3. From the C ¹³ NMR chart, a peak showing the formation of a carbonyl group can be detected in the vicinity of 203 ppm, and the following structural formula can be detected from the MS spectrum.

A spike of 344 of the starting material phenol is shown.

Subsequently, while the flask equipped with the thermometer, the cooling tube, and the stirrer was subjected to nitrogen gas filling, 84 parts (hydroxyl group: 1.0 equivalent) of the phenol compound (A-1) and 463 parts (5.0 mol) obtained in the above reaction were added. Ear) epichlorohydrin, 53 parts of n-butanol and dissolved. After the temperature was raised to 50 ° C, 220 parts (1.10 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then further reacted at 50 ° C for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 °C. Further, 300 parts of methyl isobutyl ketone and 50 parts of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 15 parts of a 10% by mass aqueous sodium hydroxide solution was added to the solution, and the mixture was reacted at 80 ° C for 2 hours, and then washed with water 100 times with 100 parts of water until the pH of the washing liquid became neutral. Subsequently, the system was dehydrated by azeotropy, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 126 parts of the objective epoxy resin (A-2). The obtained epoxy resin (A-2) had a softening point of 95 ° C (B&R method), a melt viscosity (measurement method: ICI viscosity meter method, measurement temperature: 150 ° C) of 9.0 dPa ‧ s, and an epoxy equivalent of 170 G/equivalent. The GPC chart of the obtained epoxy resin is shown in Fig. 4, the C ¹³ NMR chart is shown in Fig. 5, and the MS spectrum is shown in Fig. 6. From the C ¹³ NMR chart, a peak showing the formation of a carbonyl group was detected in the vicinity of 203 ppm, and a peak of 512 represented by the following structural formula (i-α) was detected from the MS spectrum.

Further, the epoxy resin (A-2) contains 10.5% by mass of the compound represented by the above structural formula (i-α), and 39.6% by mass of the following structural formula (i-β)

The compound shown, and 49.9 mass% of other oligomer components.

Example 2

An epoxy resin (A-3) having a target of 128 parts was obtained in the same manner as in Example 1 except that it was made into 122 parts (1.50 mol) of a 37% aqueous formaldehyde solution. The obtained epoxy resin (A-3) had a softening point of 98 ° C (B&R method), a melt viscosity (measurement method: ICI viscosity meter method, measurement temperature: 150 ° C) of 18.0 dPa·s, and an epoxy equivalent of 178. G/equivalent. The GPC chart of the obtained epoxy resin is shown in Fig. 7, the C ¹³ NMR chart is shown in Fig. 8, and the MS spectrum is shown in Fig. 9. From the C ¹³ NMR chart, a peak showing the formation of a carbonyl group was detected in the vicinity of 203 ppm, and a peak showing 512 represented by the above structural formula (i-α) was detected from the MS spectrum.

In addition, the epoxy resin (A-3) contains 15.5% by mass of the compound represented by the above structural formula (i-α), 20.7% by mass of the compound represented by the above structural formula (i-β), and 63.8% by mass or more. Oligomer component.

Examples 3, 4, and Comparative Example 1

The epoxy resin (A-2) and the epoxy resin (A-3) are used as the epoxy resin and the epoxy resin (A-4) is used [the following structural formula

The tetrafunctional naphthalene type epoxy resin ("Epiclon HP-4700" epoxy equivalent: 165 g / equivalent) made by DIC) is used as a comparative phenol novolac type phenol resin ("DIC") TD-2131", hydroxyl equivalent: 104 g/eq) as a hardener, triphenylphosphine (TPP) as a hardening accelerator and blended according to the composition shown in Table 1, and flowed into a mold of 11 cm × 9 cm × 2.4 mm, using After the press was molded at a temperature of 150 ° C for 10 minutes, the molded product was taken out from the mold, and then post-hardened at a temperature of 175 ° C for 5 hours. The heat resistance and the coefficient of linear expansion were evaluated. Further, the solvent solubility of the epoxy resin (A-2), the epoxy resin (A-3) and the epoxy resin (A-4) was measured by the following method, and the results are shown in Table 1.

<heat resistance (glass transition temperature)>

Using a viscoelasticity measuring device (DMA: Rheometric Co., Ltd. solid viscoelasticity measuring device RSAII, rectangular tension method; frequency 1 Hz, temperature rising rate 3 ° C / min), the elastic modulus was changed to the maximum (tan δ change rate was the largest) The temperature was evaluated as the glass transition temperature.

<linear expansion coefficient>

A thermomechanical analysis device (TMA: SS-6100 manufactured by Seiko Instruments Co., Ltd.) was used, and thermomechanical analysis was performed in a compression mode.

Measuring condition

Measuring frame weight: 88.8mN

Heating rate: 2 times at 3 ° C / min

Measuring temperature range: -50 ° C to 300 ° C

Each of the same samples was measured twice under the above conditions, and the average expansion coefficient of the second measurement in the temperature range from 25 ° C to 280 ° C was evaluated as a linear expansion coefficient.

<solvent solubility>

Ten parts of epoxy resin and 4.3 parts of methyl ethyl ketone were dissolved in a sample bottle in a sealed state at 60 ° C. Subsequently, it was cooled to 25 ° C to evaluate the presence or absence of precipitation of crystals. When the crystal was not precipitated, it was evaluated as ○, and when the crystal was precipitated, it was evaluated as ×.

Example 5 and Comparative Example 2

An epoxy resin, a phenol novolac type phenol resin ("TD-2090" manufactured by DIC Co., Ltd., hydroxyl equivalent: 105 g/eq) was prepared as a hardener and 2-ethyl-4- according to the formulation described in Table 2 below. Methylimidazole (2E4MZ) was prepared as a hardening accelerator by blending methyl ethyl ketone so that the nonvolatile content (NV) of the last composition was 58 mass%.

Subsequently, the laminate was produced by hardening under the following conditions, and the heat resistance and the coefficient of thermal expansion were evaluated in accordance with the following methods. The results are shown in Table 2.

<Laminated board manufacturing conditions>

Substrate: GLASSCLOTH "#2116" (210 × 280 mm) manufactured by Nitto Bose Co., Ltd.

Number of layers: 6 Pre-impregnation conditions: 160 ° C

Hardening conditions: at 200 ° C, 40 kg / cm ² , 1.5 hours, thickness after forming: 0.8 mm

<heat resistance (glass transition temperature)>

A sample of 5 mm × 54 mm × 0.8 mm was cut out from the laminate, and this was used as a test piece and a viscoelasticity measuring device (DMA: Rheometric Co., Ltd. solid viscoelasticity measuring device RSAII, rectangular tension method; frequency 1 Hz, temperature rising rate 3) was used. °C/min), the temperature at which the modulus of elasticity was changed to the maximum (the rate of change of tan δ was maximum) was evaluated as the glass transition temperature.

<linear expansion coefficient>

A sample of 5 mm × 5 mm × 0.8 mm was cut out from the laminate, and a thermomechanical analyzer (TMA: SS-6100, manufactured by Seiko Instruments Co., Ltd.) was used as a test piece, and thermomechanical analysis was performed in a compression mode.

Measuring condition

Measuring frame weight: 88.8mN

Heating rate: 2 times at 3 ° C / min

Measuring temperature range: -50 ° C to 300 ° C

Each of the same samples was measured twice under the above conditions, and the average expansion coefficient of the second measurement in the temperature range from 240 ° C to 280 ° C was evaluated as a linear expansion coefficient.

no.

Fig. 1 is a GPC chart of the phenol compound obtained in Example 1.

Fig. 2 is a ¹³ C-NMR spectrum of the phenol compound obtained in Example 1.

Fig. 3 is a mass spectrum of the phenol compound obtained in Example 1.

Fig. 4 is a GPC chart of the epoxy resin obtained in Example 1.

Fig. 5 is a ¹³ C-NMR spectrum of the epoxy resin obtained in Example 1.

Fig. 6 is a mass spectrum of the epoxy resin obtained in Example 1.

Fig. 7 is a GPC chart of the epoxy resin obtained in Example 2.

Fig. 8 is a ¹³ C-NMR spectrum of the epoxy resin obtained in Example 2.

Fig. 9 is a mass spectrum of the epoxy resin obtained in Example 2.

Claims (12)

A curable resin composition characterized by an epoxy resin (A) and a curing agent (B) having a naphthalene structure and a cyclohexadienone structure in a molecular structure. A skeleton formed by a methylene group and a glycidoxy group. The curable resin composition of claim 1, wherein the cyclohexadienone structure present in the molecular structure of the epoxy resin (A) is a 2-naphthone structure. The curable resin composition of claim 2, wherein the epoxy resin (A) contains the following structural formula (i) (In the formula, R ¹ is a compound (a) each independently exhibits a skeleton represented by a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 2 carbon atoms). The curable resin composition of claim 3, wherein the epoxy resin (A) is an epoxy equivalent of 150 to 300 g/eq. The curable resin composition of claim 2, wherein the epoxy resin (A) has 2,7-dihydroxynaphthalenes and formaldehyde, relative to 2,7-dihydroxynaphthalenes, based on Mo The ear reference is a molecular structure obtained by reacting the obtained reactant with epihalohydrin in the presence of an alkaline catalyst of 0.2 to 2.0 times. A cured product characterized in that the curable resin composition according to any one of claims 1 to 5 is hardened and reacted. A printed wiring board which is immersed in a reinforcing substrate by a resin composition which is further varnished by further mixing an organic solvent (C) with a composition according to any one of claims 1 to 5 A copper foil is obtained and heated and pressure-bonded. An epoxy resin characterized by having a skeleton in which a naphthalene structure and a cyclohexadienone structure are bonded through a methylene group and a glycidoxy group in a molecular structure. An epoxy resin according to item 8 of the patent application, which has the following structural formula (i), (In the formula, R ¹ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms). An epoxy resin characterized by the presence of 2,7-dihydroxynaphthalenes and formaldehyde in an amount of 0.2 to 2.0 times the amount of an alkaline catalyst based on a molar basis relative to 2,7-dihydroxynaphthalenes. The molecular structure obtained by reacting the resulting reactant with an epihalohydrin is carried out. The invention relates to a method for preparing an epoxy resin, characterized in that 2,7-dihydroxynaphthalenes and formaldehyde are used in an amount of 0.2 to 2.0 times based on a molar basis for 2,7-dihydroxynaphthalenes relative to 1 mole. React in the presence of a sex catalyst, and then make The resulting reactant is reacted with an epihalohydrin. The method for producing an epoxy resin according to claim 11 is obtained by using formaldehyde in an amount of 0.6 times or more based on the molar basis of 2,7-dihydroxynaphthalene.